Iminophenols as froth flotation reagents for metallic ores

ABSTRACT

A froth flotation method for the recovery of iron, copper, cobalt, nickel, and vanadium minerals from their ores over silica, alumino, and ferromagnesian silicates, which comprises subjecting the comminuted ore of aforesaid metals to froth flotation process in the presence of an effective amount of iminophenols such as methyliminodihydroxybenzoic acid, methyliminocresolcresylic acid, methyliminocresol adduct of polyethylene glycol, the indicated compounds provide sellectivity and recovery of metal values of iron, copper, cobalt, nickel, and vanadium from their oxide, silicate, sulfide, arsenide, and antimonide ores in an enriched froth concentrate of the said minerals, leaving a tailings poor in these minerals.

United States Patent 1191 Petrovich 1 June 24, 1975 IMINOPHENOLS ASFROTH F LOTATION REAGENTS FOR METALLIC ORES [76] Inventor: VojislavPetrovich, 1929 W. Schiller St., Chicago, 11].

[22] Filed: Apr. 30, 1974 21 Appl. No.: 465,412

[52] 11.8. C1. 209/166 [51] Int. Cl. B03D 1/02 [58] Field of Search209/166, l6?

[56] References Cited UNITED STATES PATENTS 2,272,489 2/1942 Ulrich260/239 E 2,296,226 9/1942 Ulrich 1. 260/239 E 2,414,199 1/1947 Gutzeit209/166 3,056,498 10/1962 De Grote... 209/166 3,425,549 2/1969Dickson,.... 209/166 3,819,048 6/1974 Weimer 209/166 PrimaryExaminer-Robert Halper [57] ABSTRACT A froth flotation method for therecovery of iron, copper, cobalt, nickel, and vanadium minerals fromtheir ores over silica, alumino, and ferromagnesian silicates, whichcomprises subjecting the comminuted ore of aforesaid metals to frothflotation process in the presence of an effective amount of iminophenolssuch as methyliminodihydroxybenzoic acid, methyliminocresolcresylicacid, methyliminocresol adduct of polyethylene glycol, the indicatedcompounds provide sellectivity and recovery of metal values of iron,copper, cobalt, nickel, and vanadium from their oxide, silicate,sulfide, arsenide, and antimonide ores in an enriched froth concentrateof the said minerals, leaving a tailings poor in these minerals.

3 Claims, No Drawings IMINOPHENOLS AS FROTH FLOTATION REAGENTS FORMETALLIC ORES This invention relates to the concentration of metalvalues from their ores. Particularly. it relates to the use ofiminophenols as flotation reagents to effect a separation of metalvalues in ores from gangue. More particularly, it relates to the use ofaryl iminophenols as froth flotation reagents for oxide ores of iron,oxide. silicate. sulfide ores of copper, oxide, silicate, sulfide.arsenide, and antimonide ores of nickel, as well as of cobalt, andvanadate of heavy metals.

The special feature of this invention using iminophenols is in thenonfloating of minerals with divalent iron. i.e.. the common sulfide ofiron as is pyrite, arsenopyrite, furthermore, ferromagnesian silicatesand the like minerals. as are garnet, biotite. chlorite, horneblende,augite. forsterite, fayalite. talc, talcy materials. and the likeminerals.

THE PREFERRED EMBODIMENTS The preferred embodiments of collectors ofthis invention are as follows:

Methyl-imino-di-hydroxybenzoic acid of the formula:

HOOC =CH Methyliminocresolcresylic acid of the formula:

H woe-OngcrgQa: cH

Methyliminocresol adduct of polyethylene glycol of the formula:

HO. lCH l O CH OH wherein n is an integer from 5 to 15.

The said iminophenol acting as froth flotation collectors, functionthrough the conjunctive action of phenolic hydroxide and imine nitrogen=N attached directly to the benzene nucleus; both groups are in alfaposition to each other. The active group of this constitution, i.e., ofaphenolic hydroxyl and an imine nitrogen are the only promoting groupsand essential part of the flotation reagent with collecting power. Allother grouping parts, i.e., the adduct of alcohol hydrocarbon group. theadduct of cresylic acid are auxiliary group ings, which aid in thebubble formation, an essentially secondary property.

The active groups are hydrophilic until promoting takes place and aid insolubility of the reagents. After promoting, the hydrophilic property ofthe active group is lost, in which case the hydrophilic part outside theactive group begins to form bubbles due to its constitution. Thus, theseiminophenols function as complete froth flotation collectors.

Although some classes of amines are known to be helpful in the recoveryof metal values by flotation. applicant has not been able to find ateaching that the iminophenols are capable of acting as flotationcollectors. However. applicant has found them to be remarkably wellsuited to flotation of certain types of ores. In fact, applicant hasdiscovered that the iminophenols are capable of collecting iron. cobalt,nickel. copper. and vanadium ores without a preflotation treatment.

Good recoveries of said metal values in respective minerals are obtainedif the reagents of the present invention are used in a circuit having apH about 8 to l2.

Further advantage ofthis invention resides in the fact that no specificfrothing agents are to be employed, since the products of this inventiondevelop sufficient froth to be good promoter and frother at the sametime, which adds in the over-all economy and operativity of the process.

The further advantage of this invention resides in the feasibility ofrecycling the processed water after desliming by cycloning, which wouldenable big savings in alkalies and ammonia.

Accordingly, a principal object of this invention is to provide a newclass of froth flotation reagents.

A further object of this invention is to provide flotation reagents withcollecting and frothing properties for collecting iron oxide ores.copper oxide, silicate, and sulfide ores, nickel as well as cobaltoxide, silicate, sulfide, arsenide. and antimonide ores, and thevanadates of heavy metals.

A still further object is to disclose the novel agents for handling oreswherein the use of activation step of any kind is unnecessary. l havediscovered that most gangue minerals are unaffected by the collector ofthis invention. Hence a method for obtaining a highly selec tiveconcentration of the desired metal values is provided.

The collectors of the invention, which function by chemical reactionwith the ore treated have complexing and presumably chelating ability atthe very surface of mineral or portion of surface of the mineralparticle of the ore treated. It is obvious that the polar part, i.e.,the complexing or chelating groups, i.e., the phenolic hydroxyl and theimine-nitrogen of the reagent are oriented towards the ore particle,while the hydroxyhydrocarbon or alkanol part of the reagent is orientedoutward from said particle. Thus the attachment of these organiccomplexing and chelating ingredients to the ore particles form a waterrepellent surface, or barrier, around at least a part of the surface ofthe ore particle and thereby facilitates the formation of the froth whenthe ore slurry is agitated in the presence of air.

The froth flotation of the present invention is carried out inaccordance with good flotation practice and usually, though not always,involves flotation in rougher cells, followed by one or severalcleanings of the rougher concentrate. The reagents are effective insmall amounts and the promotion is sufficiently persistent so that it isfeasible to carry out the rougher and cleaner flotation with a singleaddition of the reagents at the begining of the operation. On the otherhand, it is sometimes advantageous to use stage addition of reagents.Pulp densities are in general the same as in other applications of frothflotation practice, i.e., about 15 to 30 percent of solids by weight.

The flotation plant practice applying the inventors method by servingthe iminophenols for the recovery of metal values, floating thehereinbefore said ores and minerals of iron, cobalt, nickel, copper, andvanadium with aryl or aralkyl iminophenols having collecting andfrothing properties, the ore is crushed, milled and sized to at leastabout 80 to 120 mesh standard sieve, which depends on the particular oretreated. Milling to finer sizes is preferable. The crushed and sized oreis pulped and as a mineral slurry is ready for treatment in theflotation plant equipment, i.e., by passing through the conditionerwhere the collector is added. From the conditioner the pulp is pumped inthe receiving box of the first stage or the main flotation bank. In themain flotation bank the froth produced by agitation and aeration isskimmed or is overflowing in the usual manner. In most cases it isadvantageous to use multiple stage flotation process to treat theunderflow or partially metal value barren pulp to increase the degree ofseparation or to enhance the grade of recovery. Also, the use of varyingamounts of emulsifiers, dispersants, and depressants etc. in differentstages may be used to advantage to obtain the highest yield and bestseparation.

Having disclosed the novel collectors of this invention as well as thehandling of the mineral slurry, I have to say the final object of thisinvention is to provide a method for the flotation recovery of mineralscontainsieve. Transfering the sized flotation feed in the flota tionmachine, various amounts of said iminophenols for collecting purposeswere added. After this step, the pulp of mineral slurry was conditionedfor 5 minutes. The amounts of collector, as well as ammonia to make a pHof about IO to I l, are indicated in the accompaning table. Beforeskimming of the rougher concentrate the pulp of mineral slurry wasconditioned and aerated for three to five minutes. The rougherconcentrates were skimmed from about five to ten minutes and afterwardscleaned with processed water.

The flotation test of sized sample of ullmannite and chloanthite fordetermination of floatability of nickel ores: and of smaltite andlinnaeit for determination of floatability of cobalt ores; as well as ofcarnotite for determination of floatability of vanadium ores, wereaccomplished in a grams flotation cell. The feed were prepared with 5grams of a mixture of ullmannite and chloanthite, as well as 5 grams ofa mixture of smaltite and linnaeite, and 45 grams of a mixture ofpyrite, arsenopyrite, pyrrhotite, and galena as gangue materialrespectively, as well as 45 grams of a mixture of crystalline schistmaterial and sandstone as gangue material with 5 grams of carnotite. Theaddition of reagents was done dropwise. The recovery ofullmannitechloanthite; smaltite'linnaeite; and of carnotite was obtainedby microscopic count.

Ore Collector NH Assay of products treated pound per ton Feed Cone,Recovery Example Methyliminocresolcresylic acid Fe 75 Fe Fe Hematite 0.60,3 32,2 65,8 92,0

Example 2 Methylimino-di-hydroxybenzoic acid Cu Cu Cu it: Copper 0.350.3 sulfide 2.8 23.8 94,]

Example 3 Methyl iminocresol adduct Cu Cu Ft Cu copper of polyethyleneglycol 03 carbonate 0.35 Malachite 1.8 43.2 944 Example 4MethyIimino-di-hydroxybenzoic acid Cu 7: Cu Cu it c tlipper 035 0.3 51lcate 2.2 3 Chrysocolla 0 8 916 Example 5 Methylimino-di-hydroxybenzoicacid Ni 7: Ni 7r Ni Nt-sllicate 020 0.3 Gamierite 2.2 IO.4 94.2

Example 6 Melhyliminocresolcresylic acid Ni Ni ii Ni ii Ullmannlte 88.0Chloanthlte by microscopic count Example 7 Methyliminocresolcresylicacid Co 7: Co 7c Co smaltite 86.0 Lmnaelte by microscopic count Example8 Methyliminocresolcresylic acid V Z V 7: V C 92.0 arnotite bymicroscopic count ing iron, cobalt, nickel, copper, and vanadium.

The above discussion as well as the disclosure illustrate my inventionin a broad and general way; for a detailed illustration thereof theexamples of the preferred embodiments of flotation practice are setforth below.

The procedure in performing the laboratory examples for iron, nickel,and copper ores was of the same manipulation as follows: specularhematite, copper sulfide, copper silicate, copper carbonate, and nickelsilicate ore, the feed was sized to pass 100 mesh standard It is to beunderstood that the foregoing detailed discussion is for the purpose ofillustration only, and it is not intended as being limiting to thespirit or scope of the appended claims.

What I claim is:

A method of beneficiating ores selected from the groups consisting ofoxide of iron, oxide, silicate, and sulfide of copper, oxide, silicate,sulfide, arsenide, and antimonide of nickel, oxide, sulfide, arsenide,and antimonide of cobalt, the vanadate of heavy metals by frothflotation process to produce a froth concentrate of desired metal valueswhich comprises effecting the froth flotation of the said ores andminerals in the presence of methyliminodihydroxybenzoic acid ascollector in a pulp of mineral slurry having a pH of 8 to 12; andrecovering the desired metal value in an enriched froth concentrate,leaving a tailings poor in the desired metal value.

2. A method of beneficiating ores selected from the groups consisting ofoxide of iron, oxide, silicate, and sulfide of copper, oxide, silicate,sulfide, arsenide, and antimonide of nickel, oxide, sulfide, arsenide,and antimonide of cobalt, the vanadate of heavy metals by frothflotation process to produce a froth concentrate of desired metal valueswhich comprises effecting the froth flotation of the said ores andminerals in the presence of methyliminocresolcresylic acid as collectorin a pulp of mineral slurry having a pH of 8 to 12; and recovering thedesired metal value in an enriched froth concentrate, leaving a tailingspoor in the desired metal value.

3. A method of beneficiating ores selected from the groups consisting ofoxide of iron, oxide, silicate, and sulfide of copper, oxide, silicate,sulfide, arsenide, and antimonide of nickel, oxide, sulfide, arsenide,and antimonide of cobalt, the vanadate of heavy metals by frothflotation process to produce a froth concentrate of desired metal valueswhich comprises effecting the froth flotation of the said ores andminerals in the presence of methyliminocresol adduct of polyethyleneglycol as collector, said adduct having 5 to 15 methyl groups in saidpolyethylene glycol, the flotation being effected in a pulp of mineralslurry having a pH of 8 to 12; and recovering the desired metal value inan enriched froth concentrate, leaving a tailings poor in the desiredmetal value.

t i l UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N3,891,545 Dated June 24, 1975 Inventor( Voj lslav Petrovlch It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 1, lines 45 to 49, the formula should appear as shown below:

HO (CH n 0 CH O N (UH 2 Signed and Sealed this twenty-fifth Day ofNovember 1975 [SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner uj'larenrsand Trademarks

1. A METHOD OF BENEFICIATING ORES SELECTED FROM THE GROUPS CONSISTING OFOXIDE OR IRON, OXIDE, SILICATE, AND SULFIDE OF COPPER, OXIDE, SILICATE,SULFIDE, ARSENIDE, AND ANTIMONIDE OF COBALT OXIDE, SULFIDE, ARSENIDE,AND ANTIMONIDE OF COBALT, THE VANADATE OF HEAVY METALS BY FORTHFLOTATION PROCESS TO PRODUCE A FROTH CONCENTRATE OF DESIRED METAL VALUESWHICH COMPRISES EFFECTING THE FROTH FLOATION OF THE SAID ORES ANDMAINERALS IN TH PRESENCE OF METHYLIMINODIHYDROXYBENZOIC ACID ASCOLLECTOR IN A PULP OF MINERAL SLURRY HAVING A PH OF 8 TO 12; ANDRECOVERING THE, DESIRED METAL VALUE IN AN ENRICHED FROTH CONCENTRATE;LEAVING A TAILINGS POOR IN THE DESIRED METAL VALUE.
 2. A method ofbeneficiating ores selected from the groups consisting of oxide of iron,oxide, silicate, and sulfide of copper, oxide, silicate, sulfide,arsenide, and antimonide of nickel, oxide, sulfide, arsenide, andantimonide of cobalt, the vanadate of heavy metals by froth flotationprocess to produce a froth concentrate of desired metal values whichcomprises effecting the froth flotation of the said ores and minerals inthe presence of methyliminocresolcresylic acid as collector in a pulp ofmineral slurry having a pH of 8 to 12; and recovering the desired metalvalue in an enriched froth concentrate, leaving a tailings poor in thedesired metal value.
 3. A method of beneficiating ores selected from thegroups consisting of oxide of iron, oxide, silicate, and sulfide ofcopper, oxide, silicate, sulfide, arsenide, and antimonide of nickel,oxide, sulfide, arsenide, and antimonide of cobalt, the vanadate ofheavy metals by froth flotation process to produce a froth concentrateof desired metal values which comprises effecting the froth flotation ofthe said ores and minerals in the presence of methyliminocresol adductof polyethylene glycol as collector, said adduct having 5 to 15 methylgroups in said polyethylene glycol, the flotation being effected in apulp of mineral slurry having a pH of 8 to 12; and recovering thedesired metal value in an enriched froth concentrate, leaving a tailingspoor in the desired metal value.